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Enantioselectivity of chiral zirconocenes as catalysts in alkene hydro-, carbo- and cycloalumination reactions

Enantioselectivity of chiral zirconocenes as catalysts in alkene hydro-, carbo- and cycloalumination reactions
Enantioselectivity of chiral zirconocenes as catalysts in alkene hydro-, carbo- and cycloalumination reactions
Enantioselectivity of chiral Zr catalysts L1L2ZrCl2 (L1 = L2 = 1-neomenthylindenyl (Ind*), (1); L1 = Cp, L2 = Ind* (2); L1 = Cp, L2 = 1-neomenthylindenyl-4,5,6,7-tetrahydroindenyl (Cp*) (3)) in the hydro-, carbo- and cyclo-alumination of alkenes by organoaluminium compounds (OAC) (AlMe3, AlEt3, HAlBui2) has been studied. It was found that OAC type exhibits the most effect on the reactions chemo- and enantioselectivity. The reaction chemo- and enantio-selectivity depend on the catalyst structure and reaction conditions (solvent type, catalyst concentration, temperature) as well. It is shown that lack of asymmetric induction in the reaction of ?-methylstyrene hydroalumination by HAlBui2, catalyzed with complexes 1 or 3, is the result of the formation of Zr hydride complexes of different structure as reaction intermediates. MTPA was used as derivatization reagent for enantiomeric excess estimation and absolute configuration assignment of ?-chiral alcohols obtained after the oxidation and hydrolysis of reaction products. The applicability of MTPA for the assignment of chiral center absolute configuration in ?–ethyl substituted primary alcohols and ?–alkyl-1,4-butanediols was shown.
0957-4166
299-310
Parfenova, Lyudmila V.
22382afc-4fee-45fc-b0e2-feeb5a1a9b62
Berestova, Tatyana V.
a239bc2d-c2c4-45b6-ab02-9a877995a2d8
Tyumkina, Tatyana V.
4af5b88b-f27d-4207-96a6-cc4e021346d1
Kovyazin, Pavel V.
a2598e68-feaa-4fea-af3d-da36e47922ec
Khalilov, Leonard M.
48fd99b3-f32b-4a3d-b170-055874e47168
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b
Dzhemilev, Usein M.
87786dc0-61b3-4f8b-80b3-ca85e8c25c9e
Parfenova, Lyudmila V.
22382afc-4fee-45fc-b0e2-feeb5a1a9b62
Berestova, Tatyana V.
a239bc2d-c2c4-45b6-ab02-9a877995a2d8
Tyumkina, Tatyana V.
4af5b88b-f27d-4207-96a6-cc4e021346d1
Kovyazin, Pavel V.
a2598e68-feaa-4fea-af3d-da36e47922ec
Khalilov, Leonard M.
48fd99b3-f32b-4a3d-b170-055874e47168
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b
Dzhemilev, Usein M.
87786dc0-61b3-4f8b-80b3-ca85e8c25c9e

Parfenova, Lyudmila V., Berestova, Tatyana V., Tyumkina, Tatyana V., Kovyazin, Pavel V., Khalilov, Leonard M., Whitby, Richard J. and Dzhemilev, Usein M. (2010) Enantioselectivity of chiral zirconocenes as catalysts in alkene hydro-, carbo- and cycloalumination reactions. Tetrahedron: Asymmetry, 21 (3), 299-310. (doi:10.1016/j.tetasy.2010.01.001).

Record type: Article

Abstract

Enantioselectivity of chiral Zr catalysts L1L2ZrCl2 (L1 = L2 = 1-neomenthylindenyl (Ind*), (1); L1 = Cp, L2 = Ind* (2); L1 = Cp, L2 = 1-neomenthylindenyl-4,5,6,7-tetrahydroindenyl (Cp*) (3)) in the hydro-, carbo- and cyclo-alumination of alkenes by organoaluminium compounds (OAC) (AlMe3, AlEt3, HAlBui2) has been studied. It was found that OAC type exhibits the most effect on the reactions chemo- and enantioselectivity. The reaction chemo- and enantio-selectivity depend on the catalyst structure and reaction conditions (solvent type, catalyst concentration, temperature) as well. It is shown that lack of asymmetric induction in the reaction of ?-methylstyrene hydroalumination by HAlBui2, catalyzed with complexes 1 or 3, is the result of the formation of Zr hydride complexes of different structure as reaction intermediates. MTPA was used as derivatization reagent for enantiomeric excess estimation and absolute configuration assignment of ?-chiral alcohols obtained after the oxidation and hydrolysis of reaction products. The applicability of MTPA for the assignment of chiral center absolute configuration in ?–ethyl substituted primary alcohols and ?–alkyl-1,4-butanediols was shown.

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Published date: 1 March 2010

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Local EPrints ID: 147857
URI: http://eprints.soton.ac.uk/id/eprint/147857
ISSN: 0957-4166
PURE UUID: 47ad7e86-499c-4c39-847d-740c58d29631
ORCID for Richard J. Whitby: ORCID iD orcid.org/0000-0002-9891-5502

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Date deposited: 26 Apr 2010 15:06
Last modified: 26 Nov 2019 02:08

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Contributors

Author: Lyudmila V. Parfenova
Author: Tatyana V. Berestova
Author: Tatyana V. Tyumkina
Author: Pavel V. Kovyazin
Author: Leonard M. Khalilov
Author: Usein M. Dzhemilev

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